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NANOCHEMISTRY – LIBERATO MANNA NR. AVAILABLE POSITIONS: 7
Theme 1.1: Optical spectroscopy on colloidal nanocrystals and their superlattices
Tutor: Iwan Moreels
Over the past 10 years, tremendous progress has been made in synthesizing a wide variety of highquality colloidal nanocrystals (NCs). As a result, we are now able to routinely prepare bright quantum
dots with excellent color purity and well-controlled photo-emission lifetime in the visible and nearinfrared spectral range. In addition, different procedures exist to prepare metallic and heavily-doped
semiconductor NCs with a strong plasmon resonance, which offers exiting prospects to couple both
properties. Many of these materials are already produced by the IIT Nanochemistry department. In
this project, we will assemble the available NCs into thin films and binary superlattices. The main
drive will be the optical investigation the the novel nanocrystals and the resulting films, focused on
their suitability for NC-based lasers and nonlinear optical switches.
Topics of the project are:
-Fabrication of self-assembled nanocrystal films, with control over nanocrystal compositions, shape
and interparticle spacing.
-Ultrafast fluorescence spectroscopy at room and cryogenic temperature on colloidal quantum dots
and quantum dot assemblies.
-Enhancement of the linear and nonlinear optical properties by joint assembly of different
semiconductor quantum dots and/or plasmonic nanocrystals.
The student should have a degree in physics, materials science, or chemistry and a strong interest in
optical spectroscopy.
For further details concerning the research project, please contact: [email protected]
Theme 1.2: Magnetic nanoparticles for cancer stem cell targeting
Tutor: Teresa Pellegrino
The aims of this theme are to develop colloidal magnetic nanocrystals as nano-platform for a
combined cancer treatment, based on hyperthermia and drug release. The focus of the project will be
on cancer stem cells (CSCs). To achieve these goals, different activities are foreseen: i) the
identification of magnetic nanocrystals with high heat performance, synthesized by means of colloidal
methods; ii) nanoparticle functionalization with pH and thermo-responsive coatings, for the controlled
drug release upon application of intra (pH) or extracellular (temperature) stimuli; iii) stabilization of the
nanoparticles in physiological conditions; iv) functionalization of the nanoparticle surface with cell
targeting markers. These will include antibodies or cell pathways, such as “Notch and Wnt” signalling
pathways, to address the nanoparticles towards CSCs; v) in vitro study on CSCs of the stimulitriggered release of drug molecules; vi) study the effect of hyperthermia treatments operated by the
magnetic nanoparticles on CSCs; vii) combined chemo and heat treatments as a function of drug and
nanoparticle doses as well as frequency and magnetic field amplitude of the alternating magnetic field
applied. The ideal applicant should have a background in cancer stem cell research with familiarity
with chemistry subjects.
For further details concerning the research project, please contact: [email protected]
Theme 1.3: Synthesis of pH and thermo-responsive polymers and their combination with
inorganic nanoparticles for controlled drug delivery
Tutor: Teresa Pellegrino
In current anticancer chemotherapies a critical drawback is related to the drugs being delivered not
only to malignant cells. Existing treatments could be by far more efficient if the drugs could be
delivered selectively to the tumour site under defined stimuli. pH AND TERMOSENSITIVE
HYDROGELS are polymeric nano-beads that are able to undergo volume changes and thus drug
incorporation and release under the effect of physical and chemical stimuli like heat or pH. The
present PhD project will focus on the development of pH and thermo responsive polymers which can
act as nanocontainers for encapsulation, protection, and transport of chemotherapeutic agents. Also,
the inclusion of magnetic nanoparticles within the hydrogel will add two additional advantages: it will
facilitate the delivery under a magnetic field to a tumour site and at the same time, it will act as a
hyperthermia agent to heat locally the nanostructure and trigger the drug release. The candidate
should work on the preparation of pH AND TERMOSENSITIVE HYDROGELS with a control over the
size, shape, composition biodegradability and physical properties. In addition, the combination of the
polymeric nanocontainers with magnetic nanoparticles will be a key step in the fabrication of
nanostructures able to elicit combined hyperthermia and drug release. The payload, being a drug or a
short oligonucleotide sequence, will be encapsulated within the polymeric shell by tuning pH and/or
temperature of the medium and, as such, the swelling properties.
For further details concerning the research project, please contact: [email protected]
Theme 1.4: Experimental and modeling aspects of (S)TEM imaging and EEL spectroscopy of
complex semiconductor and oxide nanostructures
Tutors: Giovanni Bertoni, Rosaria Brescia
High resolution transmission electron microscopy, both in parallel and in convergent beam
configurations (TEM and STEM, respectively), is able to provide a wealth of information concerning
the structural properties of materials. In addition to the highly spatially resolved qualitative
information, quantitative structural determination can be obtained from the interpretation of images
based on modeling and simulations. This information can be coupled to the analysis of the energy
distribution of electrons after inelastic interaction with the sample via electron energy-loss
spectroscopy (EELS). The latter technique, in particular carried out at the element ionization edges, is
able to provide valuable insights concerning the local structural, chemical, and electronic properties of
individual elements at sub-nanometer resolution. The experimental results, in combination with
modeling (e.g., density functional theory, multiple scattering theory), are able to shed light on a variety
of aspects (e.g., oxidation state or valence, local chemical environment) which are useful to
understand the material properties. In particular, nanostructured systems with a broad variety of
compositions, sizes and morphologies, mostly synthesized by chemical methods, offer an interesting
field of investigation due to their tunable optical, electronic, and chemical and magnetic properties.
The aim of this project is the model-based quantitative analysis of the structural and electronic
properties of these systems, as-fabricated and after employment within chemical (e.g., ligand
exchange, catalysis for CO abatement) and electrochemical (e.g., lithium-ion batteries) processes,
which will provide helpful complementary information concerning the ongoing phenomena.
For further details concerning the research project, please contact: [email protected],
[email protected]
Theme 1.5: Novel catalytic materials based on nanocomposites for water gas shift reaction
and selective carbon monoxide oxidation
Tutors: Massimo Colombo, Liberato Manna
The aim of this theme is to develop new catalysts for CO abatement in hydrogen-rich gases for fuel
cells, produced through steam reforming of fossil fuels, alcohols or biomass. In polymer electrolyte
fuel cells, due to their low operational temperature, the platinum catalyst is likely to be poisoned by
carbon monoxide (CO), and the performance of the unit is degraded when CO is present in the
reformed gas beyond a few ppm. In general, a CO removal unit is provided downstream a reforming
unit which produces the reformed gas rich in hydrogen, and CO is selectively converted and removed
through a series of reactions (water gas shift and, e.g., selective carbon monoxide oxidation) in order
to obtain a CO concentration in the reformed gas <10 ppm. Typical catalysts for CO conversion are
based on Cu-Zn, CeO2-Au, and Fe3O4-Au. The aims here are to prepare new composite materials
made of metal oxide nanocrystals/metal domains. These composite are expected to exhibit catalytic
properties towards the water gas shift reaction and preferential CO oxidation. The steps involved will
be: (a) Synthesis of various metal-metal oxide (MO) based nanostructures (by employing both nonhydrolytic and hydrolytic methods). (b) Assembly of these A-MO heterostructures to form composite
materials. (c) Catalytic tests and catalyst characterization. The ideal applicant should have a
background in chemistry or chemical engineering with familiarity with catalysis.
For further details concerning the research project, please contact: [email protected];
[email protected]
Theme 1.6: Nanoparticles for energy storage applications
Tutor: Liberato Manna, Luca De Trizio
The aim of this research theme is to develop nanocrystals based composite materials for energy
storage application. The emphasis will be on lithium ion battery applications, for which one key step is
to identify novel candidate nanoscale materials for the electrodes. The focus will be mainly on
nanoscale layered materials, such as transition metal dichalcogenides and layered metal oxides,
which are capable of hosting lithium in between the layers. We will develop colloidal synthesis
approaches for these compounds, which will be first of all studied in detail for what concerns their
optical, structural, electronic and electrical transport properties. In addition, electrochemical studies
will be carried out at every stage of the project, starting from the as-prepared nanocrystals up to the
final battery assembly. The successful candidate for this theme should have a strong background in
disciplines such as Materials Science, Chemistry or Chemical Engineering.
For further details concerning the research project, please contact: [email protected];
[email protected]
Theme 1.7: Study of the chemical transformations in nanocrystals for applications in
plasmonics and photovoltaics
Tutor: Liberato Manna, Yi Xie
The aim of this research theme is to study chemical transformations in nanocrystals in order to
prepare nanoscale materials with finely tuned properties, for applications in both plasmonics and
photovoltaics. One example is represented by cation exchange reactions, which involve partial or
complete replacement of the sublattice of cations in a crystal with a new sublattice of different cations,
while the sublattice of anions remains in place. Another example is represented by oxidation/
reduction processes which can alter the chemical composition of a nanocrystal, which in turn will
impact its electronic properties. It is possible to exploit these reactions and their combination, to
access nanocrystals of materials that are difficult to prepare via direct synthesis or for which these
reactions provide a means for fine tuning of the chemical composition. Two main classes of
compounds will be studied: binary copper chalcogenide nanocrystals, in which the copper
stoichiometry regulates their plasmonic behavior, and ternary and quaternary semiconductor
nanocrystals, in which the relative stoichiometric ratios of the various cations in the lattice regulate the
band gap of the material. The project involves the colloidal synthesis of nanocrystals, the study of
their transformations by means of various techniques (spectroscopy, electrochemistry, electron
microscopy with all its ancillary in-situ techniques, X-ray diffraction), and the study of the properties of
the final particles. For plasmonic materials, this will include the identification of the active plasmonic
modes, the study of the plasmon dynamics and the investigation of the near field properties. For
photovoltaic materials, this will include the analysis of their optical and transport properties (both in
the dark and under illumination) and their testing as active materials in prototype photovoltaic
devices. To this aim, the project foresees the development of procedures to exchange the native
surfactant stabilizers with carbon-free ligands, with the aim of having final nanocrystal-based cells
characterized by high power conversion efficiency.
For further details concerning the research project, please contact: [email protected];
[email protected]